DE60015606T2 - COMPOSITIONS CONTAINING AMINOUS ANTIOXIDANTS BASED ON N- (4-ANILINOPHENYL) AMIDES - Google Patents

Abstract

A composition of matter is disclosed wherein the composition comprises an N-aromatic substituted acid amide compound selected from the group consisting of compounds of formula (I) wherein A and B are independently selected alkylene groups; R<SUB>1 </SUB>is selected from the group consisting of hydrogen, alkyl, alkylether, or ester; R<SUB>2 </SUB>is hydrogen if R<SUB>1 </SUB>is hydrogen; R<SUB>2 </SUB>is an alkyl primary amine if R<SUB>1 </SUB>is alkyl, alkylether, or ester; R<SUB>3 </SUB>and R<SUB>4 </SUB>are independently selected from the group consisting of hydrogen and alkyl; R<SUB>5 </SUB>is a sterically hindered phenolic group of formula (II) or formula (III) wherein X is CH<SUB>2</SUB>, S, NH, or O; and m, n, and p are independently selected integers equal to 0 or 1. These compositions may be used as such or they may be bound to a polymer backbone via a linking moiety. In either case, they are useful as antioxidants, particularly in lubricating oil compositions

Description

1st area the invention

The present invention relates to the protection of organic materials, such as rubber, plastic, lubricating oils, petroleum fuels, and waxes organic liquids against oxidation by using antioxidants, which are N-aromatic substituted acid amide compounds.

In a preferred embodiment The present invention relates to lubricants, in particular lubricating oils. Especially For example, the present invention relates to a class of dispersant additives with antioxidant properties and the ability to improve the Viscosity index, preferably from an ethylene-propylene modified diene terpolymer (EPDM) or an ethylene-propylene copolymer and derived from an N-aromatic substituted acid amide compound are.

2. Description of the state of the technique

organic Materials such as rubber, plastic, lubricating oils, petroleum fuels, waxes and organic liquids require known a protection against oxidation.

Present are many of these organic materials have higher operating temperatures and subjected to a strong mechanical shear stress. New Stabilizer containing organic materials before a premature Oxidation and degradation under these harsher operating conditions can be searched.

Of Further, numerous attempts have been made in the development of lubricating oils. To provide additives which are a lubricating oil with dispersing properties of mud and soot as well provide a high temperature deposition control. Furthermore is the formulation of an oil, that the requirements regarding High and low temperature viscosity Fulfills, critical and in most cases becomes a viscosity index Improving means used to achieve this goal. The most of the prior art multifunctional additives one or two of these features.

It is well known that internal combustion engines in a wide Temperature range including a low-temperature stop-and-go operation and high-temperature conditions, which is generated by continuous driving at high speed will be operated. A stop-and-go driving especially under Cold, humid weather conditions lead to the formation of mud in the crankcase and in the oil pipes a gasoline or diesel engine. This mud severely limits the ability a crankcase engine oil for effective Lubrication of the engine. About that In addition, the mud with the water trapped in it can do so contribute to rust in the engine. These problems can be caused by Recommendations of engine manufacturers regarding oil service, which typically longer oil drain intervals or Specify change intervals, reinforced become.

additives the engines opposite to prevent mud formation, generally contain nitrogen. These additives are also called Dispersants and / or detergents in the formulation of Crankcase lubricating oil compositions known. The preparation of many of the known dispersant / detergent compounds based on the reaction of an alkenyl succinic acid or anhydride thereof with an amine or polyamine to form an alkenyl succinimide or an alkenylsuccinamic acid or an anhydride as an intermediate. This is advantageous as these products, if not completely with an amine or polyamine be converted, rust in the engine can form.

It is general practice, the alkenyl group either before or after Reaction with an acid anhydride but to chlorinate before the reaction with the amine or polyamine, to produce a reaction product in which a portion of the amine or polyamine is bonded directly to the alkenyl moiety. The conviction In many of these methods, a product with a relatively high is Nitrogen content to produce improved dispersing properties to deliver. However, chlorine is undesirable from an environmental point of view By-product of such processes and it would be advantageous to have relatively high Nitrogen levels without the use of chlorine to achieve.

Ethylene-propylene copolymers and ethylene-α-olefin-nonconjugated diene terpolymers which have been grafted and derivatized to provide valuable properties in lubricating oil compositions well known.

Aralkyl-substituted diarylamines, such as 4,4'-bis (α, α-dimethylbenzyl) diphenylamine (NAUGARD 445, Uniroyal Chemical) and their use as antioxidants for a variety of polymeric materials are known from the US 3 452 056 A and US Pat. No. 3,505,225 known.

In addition, aromatic amines have been used as stabilizers of organic materials, especially for use in plastics, rubber and oils. For example, this describes US Pat. No. 3,505,225 aromatic amine antioxidants based on α-methylstyryl-substituted diphenylamines.

The US 3,522,180 A. discloses a process for producing an ethylene-propylene copolymer substrate effective as a viscosity index improver for lubricating oils.

The US 4,026,809 A discloses graft copolymers of a methacrylate ester and an ethylene-propylene-alkylene norbornene terpolymer as a viscosity index improver for lubricating oils.

The US 4 089 794 A discloses ethylene copolymers derived from ethylene and one or more C ₃ -C ₂₈ alpha-olefins, which copolymers are solution-grafted with an ethylenically unsaturated carboxylic acid material, followed by reaction with a polyfunctional material, such as a polyamine, a polyol, or a Hydroxylamine, which is able to react with the carboxyl groups of the acid.

The US 4 096 319 A discloses polymers with anti-oxidant functionality which are said to be useful as viscosity index (VI) improvers for high temperature operation. The antioxidant moiety is intended to prevent extensive oxidative degradation of the polymer, thereby rendering the polymers particularly useful in lubricating oils used in diesel engines. A method for producing the antioxidant-containing VI improvement polymer by esterifying a carboxylic acid-containing polymer with an N-methylhydroxyethylamide-containing antioxidant is also disclosed.

The US 4 137 185 A and US 4,144,181 A disclose an oil soluble derivatized ethylene copolymer derived from about 2 to 98 weight percent ethylene and one or more C _{3 to} C ₂₈ α-olefins, for example, propylene. These compounds are preferably solution-grafted with an ethylenically unsaturated dicarboxylic acid material under an inert atmosphere and at elevated temperature in the presence of a high temperature decomposable free-radical-forming initiator. Thereafter, the graft copolymer is reacted with a polyamine having at least two primary amine groups, eg, an alkylene polyamine, such as diethylene triamine, to form a carboxyl-grafted polymeric imide, usually maleimide derivatives. The derivatives are reacted with an anhydride of a C ₁ -C ₃₀ hydrocarbyl substituted acid, preferably acetic anhydride, to form an oil soluble stable amide derivative of the polyamine which exhibits a minimal change in viscosity over an extended period of time. Suitable number average molecular weights (M _n ) of the copolymers range from about 700 to 500,000. When the molecular weight is in the range of 10,000 to 500,000, these copolymers are also useful as multifunctional viscosity index improving agents.

The US 4 146 489 A discloses graft copolymers wherein the backbone polymer is a rubbery oil-soluble ethylene-propylene copolymer or ethylene-propylene modified diene terpolymer and the grafting monomer is a C-vinylpyridine or N-vinylpyrrolidone which provides a combined improvement in viscosity index to the hydrocarbon fuel dispersing properties and lubricating oils for internal combustion engines and impart dispersant properties. The graft copolymers are prepared by intimately admixing the backbone polymer, the grafted monomer, and a free radical initiator at a temperature below the initiation temperature, followed by a temperature increase to or above the initiation temperature, thereby providing a product containing little or no by-product.

The US 4 234 435 A discloses carboxylic acid acylating agents derived from polyalkylenes and a carboxyl reactant having a molecular weight of about 1,300 to 5,000 and at least 1.3 carboxyl groups per polyalkylene equivalent.

The US 4 320 019 A discloses a multi-purpose lubricating additive prepared by reacting a mixed polymer of ethylene and a C ₃ -C ₈ alpha-monoolefin with an olefinic carboxylic acid acylating agent to form an acylation reaction intermediate, which is subsequently reacted with an amine.

The US 4 340 689 A discloses a process for grafting a functional organic group onto an ethylene copolymer or ethylene-propylene-diene terpolymer.

The US 4,357,250 discloses a reaction product of a copolymer and an olefin carboxylic acid via an "ene" reaction, followed by reaction with a monoamine polyamine mixture.

The US 4,382,007 A discloses a dispersant / viscosity index improving agent prepared by reacting a polyamine-derived dispersant with an oxidized ethylene-propylene polymer or an ethylene-propylene-diene terpolymer.

The US 4,668,834 discloses low molecular weight copolymers of ethylene, an alpha-olefin and optionally a non-conjugated polyene having a viscosity index of at least about 75 and vinylidene-type unsaturated bond. The copolymers are said to have unenrouted benefits as intermediates in epoxy grafted electrical encapsulant compositions.

The US Pat. No. 4,797,511 and US 4,837,259 A describe synergistic mixtures of hindered phenols and amine antioxidants as stabilizers for polypropylene and polyethylene.

The US 4,863,623 A discloses multifunctional grafted and derivatized copolymers which provide a viscosity index improving property, dispersant properties and antioxidant properties in a multi-grade lubricating oil composition. The additive composition comprises a grafted and amine-derivatized copolymer made from ethylene and at least one C ₃ -C ₁₀ α-monoolefin and optionally a polyene selected from non-conjugated dienes and trienes, and from about 15 to 80 mole percent ethylene , about 20 to 85 mole% of the C ₃ -C ₁₀ α-monoolefin and about 0 to 15 mole% of the polyene having an average molecular weight in the range of about 5,000 to 500,000, and having at least one olefinic carboxylic acid acylating agent to one or has been converted to a plurality of acylation reaction intermediates, characterized in that they have a carboxylic acid acylating function in their structure, and the reaction intermediate is reacted with an aminoaromatic polyamine compound. The aminoaromatic polyamine compound is selected from the group consisting of an N-arylphenylenediamine, an aminothiazole, an aminocarbazole, an aminoindole, an aminopyrrole, an aminoindazolinone, an aminomercaptotriazole, and an aminoperimidine to form the grafted and amine-derivatized copolymer. A lubricating oil composition containing the additive is also disclosed.

The US 4 904 403 A discloses compounds derived from 2,5-dimercapto-1,3,4-thiadiazole and one or two moles of polyolefin having from 5 to 400 carbon atoms. The 5-position of the 2-mercapto-1,3,4-thiadiazole may be substituted by an alkylthio, a 2-hydroxyalkylthio, an amino or a hydroxy group. The compounds are said to be effective as dispersants, anti-wear agents and anti-oxidants when incorporated into lubricating compositions.

• (1) ein Gemisch eines gepfropften und derivatisierten Polymers und eines Mineralöls mit Schmierviskosität, wobei das Gemisch etwa 5 bis 35 Gew.-% des Polymers und zum Rest das Mineralöl umfasst, und eine als kinematische Viskosität bei 100°C gemessene Volumenviskosität von mehr als etwa 2.000 Centistoke aufweist, und
• (2) eine geringfügige Menge eines Colösemittels definierter Struktur, das in wirksamer Weise die Volumenviskosität des Gemisches merklich verringert, umfasst.

The US 4,990,274 A discloses an oil additive composition which

• (1) a mixture of a grafted and derivatized polymer and a mineral oil of lubricating viscosity, wherein the mixture comprises about 5 to 35% by weight of the polymer and the remainder the mineral oil, and a volumetric viscosity of more than 100% measured as kinematic viscosity at 100 ° C has about 2,000 Centistoke, and
• (2) a minor amount of a cosolvent of defined structure which effectively reduces the bulk viscosity of the mixture appreciably.

The US 5 021 177 A discloses a dispersant / viscosity index improver for lubricating oils containing an EPR or EPT polymer to which an isocyanatoethyl methacrylate has been graft-polymerized and which has subsequently been reacted with N-phenyl-p-phenylenediamine.

The US 5 047 530 A discloses tris (N-alkyl-p-phenylenediamino) -1,3,5-triazine compounds useful as antiozonants for unsaturated high polymeric agents. The compounds can be prepared by reacting an N-alkylphenylenediamine with a cyanuric halide.

The US 5 075 383 A discloses an additive composition comprising a grafted and amine-derivatized copolymer prepared from ethylene and at least one C ₃ -C ₁₀ α-monoolefin and optionally a polyene selected from non-conjugated dienes and trienes and about 15 to 80 moles % Ethylene, about 20 to 85 mole percent of the C ₃ -C ₁₀ alpha-monoolefin, and about 0 to 15 mole percent of the polyene summarizes. The copolymer has an average molecular weight in the range of about 5,500 to 50,000, with at least 1.8 molecules of a carboxylic acid acylating function grafted onto the copolymer per molecule of the copolymer. The grafted copolymer is reacted with an aminoaromatic polyamine compound selected from the group consisting of an N-arylphenylenediamine, an aminocarbazole and an amino-perimidine to form the grafted and amine-derivatized copolymer. A lubricating oil composition containing the additive is also disclosed.

The US 5 094 766 A discloses dispersants, antioxidants, and viscosity index improvers for lubricating oils containing an EPR or EPT polymer to which vinyl azlactone has been graft-polymerized and which has subsequently been reacted with an N-phenyl-p-phenylenediamine.

The US 5 120 844 A discloses trisubstituted 1,3,5-triazine compounds having at least one (N-alkyl-p-phenylenediamino) group on the triazine ring. The preferred compositions are trisubstituted with the alkyl p-phenylenediamino group. The preferred compounds can be prepared by reacting an N-alkylphenylenediamine with a cyanuric halide.

The US 5,162,086 A discloses an additive composition comprising a grafted and amine-derivatized copolymer prepared from ethylene and at least one C ₃ -C ₁₀ α-monoolefin and optionally a polyene selected from non-conjugated dienes and trienes and about 15 to 80 moles % Ethylene, about 20 to 85 mole percent of the C ₃ -C ₁₀ alpha-monoolefin, and about 0 to 15 mole percent of the polyene. The copolymer has a number average molecular weight in the range of about 5,500 to 50,000 with at least 1.8 molecules of a carboxylic acid acylating function grafted onto the copolymer per molecule of the copolymer. The grafted copolymer is reacted with an amine substituted phenothiazine to form the grafted amine derivatized copolymer. A lubricating oil composition containing the additive is also disclosed.

The US 5 188 745 A discloses an additive composition comprising a grafted and amine derivatized copolymer prepared from ethylene and at least one C ₃ -C ₁₀ α-monoolefin and optionally a polyene, wherein the polyene is selected from non-conjugated dienes and trienes and the copolymer about 15 to 80 mole percent ethylene, about 20 to 85 mole percent of the C ₃ -C ₁₀ alpha-monoolefin, and about 0 to 15 mole percent of the polyene. The copolymer has a number average molecular weight in the range of about 5,500 to 500,000 and has been reacted with at least one olefinic carboxylic acid acylating agent to form one or more acylation reaction intermediates characterized by having a carboxylic acid acylating function in their structure. This reaction intermediate is then reacted with an N- (2-aminoalkyl) imidazolidone to form the grafted derivatized copolymer. A lubricating oil composition containing the additive is also disclosed.

The US 5 200 102 A discloses an additive composition comprising a grafted and derivatized copolymer prepared from ethylene and at least one C ₃ -C ₁₀ α-monoolefin and optionally a polyene selected from non-conjugated dienes and trienes, the copolymer having about 15 to 80 molar molecular weight. % Ethylene, about 20 to 85 mole percent of the C ₃ -C ₁₀ alpha-monoolefin, and about 0 to 15 mole percent of the polyene and has an average molecular weight in the range of about 5,000 to 500,000, with at least one olefinic Carboxylic acid acylating agent, to form one or more acylating reaction intermediates characterized by having a carboxylic acid acylating function in their structure. The reaction intermediate is reacted with an aminoalkylthiothiadiazole to form the grafted derivatized copolymer. A lubricating oil composition containing the grafted derivatized copolymer is also disclosed.

The US 5,474,694 A discloses an additive composition comprising a grafted and amine derivatized copolymer prepared from ethylene and at least one C ₃ -C ₁₀ alpha-monoolefin and optionally a polyene selected from non-conjugated dienes and trienes, the copolymer being about 15 to 80 Mole% ethylene, about 20 to 85 mole% of the C ₃ -C ₁₀ α-monoolefin, and about 0 to 15 mole% of the polyene. The copolymer has a number average molecular weight in the range of about 5,500 to 50,000m, with at least 1.8 molecules of a carboxylic acid acylating function grafted onto the copolymer per molecule of the copolymer. The grafted copolymer is reacted with one of a 2-anilinoalcohol, a (2-hydroxyalkyl) pyridine, a 4- (2-hydroxyalkyl) morpholine, a 1- (2-hydroxyalkyl) piperazine and a 1- (2-hydroxyalkyl) -2 -pyrrolidine selected aminoalcohol compound reacted.

The US 5 556 923 A discloses a continuous process for making adduct formation A derivatized EPM or EPDM oil solution wherein a grafted ethylene polymer is subjected to an antioxidant-forming diamine to form an adduct while maintaining an adducting reaction.

The US Pat. No. 5,698,500 discloses a graft copolymer comprising a copolymerization of a mixture of monomers comprising ethylene, a C ₃ -C ₁₂ alpha-monoolefin and a polyene which is a member selected from non-conjugated dienes and trienes , was produced. To the copolymer is grafted a 2-mercapto-1,3,4-thiadiazole unit. Lubricating oil additives and lubricating oils comprising the graft copolymer are also disclosed.

The US 5,747,433 A discloses a composition of from about 2 to about 20% of a hydrogenated diene / vinyl aromatic block copolymer and a nonionic surfactant which is soluble in the oil and comprises at least one ester or ether group in a medium of oil of lubricating viscosity compared with comparable compositions without the surfactant should have a reduced viscosity.

The US 5,834,544 discloses compounds having two substitutions of an aromatic amine functionality and a hindered phenol functionality which are useful as stabilizers for organic materials.

The US 6 107 257 A discloses an additive comprising a highly grafted multifunctional olefin copolymer comprising a grafted and amine derivatized copolymer prepared from ethylene and at least one C ₃ -C ₂₃ α-monoolefin and optionally a polyene, said copolymer of ethylene and at least one C ₃ -C ₂₃ α-monoolefin having 0.3 to 0.75 carboxylic acid groups per 1000 number average molecular weight units of the olefin copolymer is grafted and wherein the olefin copolymer has a number average molecular weight between 20,000 and 150,000, and lubricating oil concentrates and compositions containing them.

The US 6 107 258 A discloses a multifunctional fuel and lubricant additive intended to provide dispersing properties as well as the benefit of viscosity index improvement, fuel economy properties, and low temperature viscometric properties. Concentrates, fuel and lubricating oil compositions containing this additive are also disclosed.

The US 6 117 825 A discloses a lubricating oil composition comprising (a) a large amount of an oil of lubricating viscosity and (b) a minor amount of dispersant of a synergistic combination of an antioxidant / dispersant additive and a dispersant additive, the combination comprising (i) a polyisobutylene succinimide and (ii) a Ethylene propylene succinimide includes.

The EP 0 922 752 A2 discloses an olefin copolymer comprising the reaction product of an acylated olefin copolymer and a polyamine, wherein the acylated olefin copolymer comprises an olefin copolymer grafted with from 0.3 to 0.75 carboxylic acid groups per 1,000 number average molecular units of the olefin copolymer, and wherein the olefin copolymer has a number average molecular weight of 20,000 up to 150,000. The copolymer is used as an additive in lubricating oil compositions where it functions as a viscosity modifier.

Summary of the invention

The The object of the present invention is a new antioxidant for the protection of organic materials, such as rubber, plastic, Lubricating oils, Petroleum fuels Waxing and organic liquids provide.

A Another object of the present invention is to provide a novel antioxidant-bound To provide a copolymer composition containing the new antioxidant as a unit thereof.

A Another object of the present invention is to provide a lubricating additive to provide a lubricating oil composition with properties in terms of providing a viscosity index, dispersing properties and can impart antioxidant properties.

These and other objects which will be apparent to those skilled in the art are provided by the present invention, which is directed to a class of antioxidant / dis percolating additives with advantages in terms of the improvement of the viscosity index, which are suitable as such or in a form attached to a polymer backbone, for example to an EPDM copolymer.

worin
A und B unabhängig voneinander aus Alkylengruppen ausgewählt sind;
R₁ aus der Gruppe ausgewählt ist, die aus Wasserstoff, Alkyl, Alkylether oder Ester besteht;
R₂ für Wasserstoff steht, wenn R₁ Wasserstoff ist;
R₂ ein primäres Alkylamin bedeutet, wenn R₁ Alkyl, Alkylether oder Ester ist;
R₃ und R₄ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus Wasserstoff und Alkyl besteht;
R₅ für eine sterisch gehinderte Phenolgruppe,

oder für

steht, worin
X CH₂, S, NH oder O bedeutet; und
m, n und p unabhängig voneinander aus ganzen Zahlen ausgewählt sind, die gleich 0 oder 1 sind.More particularly, the present invention relates to a composition comprising an N-aromatic substituted acid amide compound selected from the group consisting of compounds represented by the formula:

wherein
A and B are independently selected from alkylene groups;
R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters;
R _{2 is} hydrogen when R _{1 is} hydrogen;
R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester;
R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl;
R _{5 represents} a sterically hindered phenol group,

or for

stands in which
X is CH ₂ , S, NH or O; and
m, n and p are independently selected from integers equal to 0 or 1.

It It should be noted here that any use of the term "alkyl" in the context of a Starting material or the end products of the present invention linear or branched cycloalkyl structures and alkyl-substituted Cycloalkyl structures, for example cyclopentyl, Cyclohexyl, 4-methylcyclohexyl and the like.

worin
A und B unabhängig voneinander aus Alkylengruppen ausgewählt sind;
R₁ aus der Gruppe ausgewählt ist, die aus Wasserstoff, Alkyl, Alkylether oder Ester besteht;
R₂ für Wasserstoff steht, wenn R, Wasserstoff ist;
R₂ ein primäres Alkylamin bedeutet, wenn R₁ Alkyl, Alkylether oder Ester ist;
R₃ und R₄ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus Wasserstoff und Alkyl besteht;
R₅ für eine sterisch gehinderte Phenolgruppe,

oder für

steht,
worin
X CH₂, S, NH oder O bedeutet; und
m, n und p unabhängig voneinander aus ganzen Zahlen ausgewählt sind, die gleich 0 oder 1 sind. Gegenstand eines weiteren Aspekts der vorliegenden Erfindung ist eine Schmierölzusammensetzung, die einen Hauptteil eines Schmieröls und einen geringfügigen Teil eines Additivs umfasst, bei dem es sich um eine N-aromatische substituierte Säureamidverbindung oder das Reaktionsprodukt aus einem an ein im Wesentlichen lineares Polymer, Copolymer oder Terpolymer gebundenen Carbonsäurematerial, das des Weiteren mit einer N-aromatischen substituierten Säureamideinheit umgesetzt wurde, handelt, wobei das N-aromatische substituierte Säureamid aus der Gruppe ausgewählt ist, die aus Verbindungen der folgenden Formel besteht:

worin
A und B unabhängig voneinander aus Alkylengruppen ausgewählt sind;
R₁ aus der Gruppe ausgewählt ist, die aus Wasserstoff, Alkyl, Alkylether oder Ester besteht;
R₂ für Wasserstoff steht, wenn R₁ Wasserstoff ist;
R₂ ein primäres Alkylamin bedeutet, wenn R₁ Alkyl, Alkylether oder Ester ist;
R₃ und R₄ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus Wasserstoff und Alkyl besteht;
R₅ für eine sterisch gehinderte Phenolgruppe,

worin
X CH₂, S, NH oder O bedeutet; und
m, n und p unabhängig voneinander aus ganzen Zahlen ausgewählt sind, die gleich 0 oder 1 sind. Gegenstand eines weiteren Aspekts der vorliegenden Erfindung ist eine Zusammensetzung, die eine Lösung umfasst, die die folgenden Bestandteile umfasst:
A) ein Reaktionsprodukt aus einem an ein im Wesentlichen lineares Polymer, Copolymer oder Terpolymer gebundenen Carbonsäurematerial, das des Weiteren mit einem N-Alkylimidazol umgesetzt ist,
B) und ein Öllösemittel und
C) ein Colösemittel, das ein Alkyl-, Dialkyl- oder gemischtes Dialkylphenol umfasst, wobei die Alkylgruppe aus der Gruppe ausgewählt ist, die aus Alkylresten mit 6 bis 22 Kohlenstoffatomen besteht.A further aspect of the present invention is the reaction product of a carboxylic acid material bonded to a substantially linear polymer, copolymer or terpolymer, further reacted with an N-aromatic substituted amic acid moiety selected from the group consisting of compounds of the following Formula consists of:

wherein
A and B are independently selected from alkylene groups;
R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters;
R _{2 is} hydrogen when R is hydrogen;
R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester;
R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl;
R _{5 represents} a sterically hindered phenol group,

or for

stands,
wherein
X is CH ₂ , S, NH or O; and
m, n and p are independently selected from integers equal to 0 or 1. A further aspect of the present invention is a lubricating oil composition comprising a major portion of a lubricating oil and a minor portion of an additive which is an N-aromatic substituted acid amide compound or the reaction product of a substantially linear polymer, copolymer or terpolymer bonded carboxylic acid material further reacted with an N-aromatic substituted acid amide unit, wherein the N-aromatic substituted acid amide is selected from the group consisting of compounds of the following formula:

wherein
A and B are independently selected from alkylene groups;
R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters;
R _{2 is} hydrogen when R _{1 is} hydrogen;
R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester;
R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl;
R _{5 represents} a sterically hindered phenol group,

wherein
X is CH ₂ , S, NH or O; and
m, n and p are independently selected from integers equal to 0 or 1. object Another aspect of the present invention is a composition comprising a solution comprising the following components:
A) a reaction product of a carboxylic acid material bonded to a substantially linear polymer, copolymer or terpolymer further reacted with an N-alkylimidazole,
B) and an oil solvent and
C) a cosolvent comprising an alkyl, dialkyl or mixed dialkylphenol, wherein the alkyl group is selected from the group consisting of alkyl groups of 6 to 22 carbon atoms.

Description of the preferred embodiments

worin
A und B unabhängig voneinander aus Alkylengruppen ausgewählt sind;
R₁ aus der Gruppe ausgewählt ist, die aus Wasserstoff, Alkyl, Alkylether oder Ester besteht;
R₂ für Wasserstoff steht, wenn R₁ Wasserstoff ist;
R₂ ein primäres Alkylamin bedeutet, wenn R₁ Alkyl, Alkylether oder Ester ist;
R₃ und R₄ unabhängig voneinander aus der Gruppe ausgewählt sind, die aus Wasserstoff und Alkyl besteht;
R₅ für eine sterisch gehinderte Phenolgruppe,

steht,
worin
X CH₂, S, NH oder O bedeutet; und
m, n und p unabhängig voneinander aus ganzen Zahlen ausgewählt sind, die gleich 0 oder 1 sind. Diese Verbindungen können als solche verwendet oder mit einem an einem im Wesentlichen lineares Polymer, Copolymer oder Terpolymer gebundenen Carbonsäurematerial umgesetzt werden. Es wird erwartet, dass sich derartige Verbindung als Antioxidationsmittel in kompoundierten Reifen, Polyolen, Kunststoffen, Urethanen, Fetten, Motorölen, Kauschukbändern, Kabeln, Dichtungen, Dichtmaterialien und Kautschukprodukten in der Kleidungs- und Teppichindustrie eignen. Bei Bindung an ein Kohlenstoff-Kohlenstoffpolymergerüst wird erwartet, dass sie sich für Produkte eignen, die an Polymere über Polymer-gebundene Verknüpfungsgruppen, wie Bernsteinsäure- oder Maleinsäureanhydrid und Epoxide, gebundene Antioxidationsmittel erfordern, um ein Antioxidationsmittel-Ausblühen (siehe beispielsweise J.A. Kuczkowski et al., Rubber Chemistry and Technology 57: 621 (1984)) aus dem Substrat zu verhindern oder um die Polymereigenschaften zu verbessern. Beispiele für Produkte, die Polymer-gebundene Antioxidationsmittel verwenden können, sind Automobilreifen, Getränkeflaschen und Automobilmotorölpolymeradditive (siehe beispielsweise M.K. Mishra et al., Polym. Sci., {Symp. Proc. Polym. '91}, Vol. 2, 694 bis 699. Veröffentlicher: Tata McGraw-Hill, Neu Delhi, Indien), wie Dispergiermittel und den Viskositätsindex verbessernde Mittel (siehe beispielsweise europäische Patentanmeldung EP 98 310 091.8 und US 5 075 383 A und US 4 863 623 A ). Bezüglich Dispergiermitteln kann die Verwendung von Colösemitteln zur Steuerung der Produktviskosität und die Verwendung in Herstellungsverfahren (siehe US 4 990 274 A und US 5 556 923 A ) bei diesen neuen derivatisierenden Antioxidationsmittelaminen auch erfolgen.As stated above, in a preferred embodiment, the present invention is directed to N-aromatic substituted acid amide compounds selected from the group consisting of compounds of the formula:

wherein
A and B are independently selected from alkylene groups;
R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters;
R _{2 is} hydrogen when R _{1 is} hydrogen;
R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester;
R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl;
R _{5 represents} a sterically hindered phenol group,

stands,
wherein
X is CH ₂ , S, NH or O; and
m, n and p are independently selected from integers equal to 0 or 1. These compounds may be used as such or reacted with a carboxylic acid material attached to a substantially linear polymer, copolymer or terpolymer. Such compounds are expected to be useful as antioxidants in compounded tires, polyols, plastics, urethanes, fats, motor oils, rubberized tapes, cables, gaskets, sealants, and rubber products in the garment and carpet industry. Binding to a carbon-carbon polymer backbone is expected to be useful for products requiring polymers bound via polymer-linked linking groups, such as succinic or maleic anhydride and epoxides, bound antioxidants to provide antioxidant blooming (see, for example, JA Kuczkowski et al ., Rubber Chemistry and Technology 57: 621 (1984)) from the substrate or to improve the polymer properties. Examples of products that can use polymer-bound antioxidants are automotive tires, beverage bottles and automotive motor oil polymer additives (see, for example, MK Mishra et al., Polym Sci., (Symp. Proc. Polym. '91), Vol. 2, 694-699 Publication: Tata McGraw-Hill, New Delhi, India), such as dispersants and viscosity index improvers (see, for example, European Patent Application EP 98 310 091.8 and US 5 075 383 A and US 4,863,623 A ). With regard to dispersants, the use of Co-solvents for controlling product viscosity and use in manufacturing processes (see US 4,990,274 A and US 5 556 923 A ) also occur with these new derivatizing antioxidant amines.

In the above structural formula wherein each of R ₁ , R ₃ and / or R _{4 is} alkyl, these are preferably alkyl of 1 to 22 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, doeicosyl or isomers thereof, for example isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl and like. More preferably R ₁ , when alkyl, is an alkyl of 8 to 18 carbon atoms, and most preferably 8 to 14 carbon atoms. It is more preferred that R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl of 1 to 6 carbon atoms, most preferably R _{3 is} alkyl of 1 to 6 carbon atoms and R _{4 is} hydrogen , Similarly, when R _{2 is} a primary alkylamine, the alkyl portion thereof is preferably alkyl of 1 to 22 carbon atoms, wherein each carbon-carbon chain may be either linear or branched.

If B is present in the molecule, these are preferably alkylene having 1 to 22 carbon atoms, for example methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, tridecylene, tetradecylene, Pentadecylene, hexadecylene, heptadecylene, octadecylene, nonadecylene, eicosylene, uneicosylene, doeicosylene and isomers thereof, that is, they may be unbranched or branched, for example, isopropylene, isobutylene, 2-ethylhexylene and the like. It is more preferable that it is an alkylene having 1 to 12 carbon atoms, especially one having 1 to 6 carbon atoms. When B is present, it is preferably methylene. One skilled in the art will understand that these structures are, for example, -CH ₂ -, -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -CH ₂ -, etc.

Similarly, when R _{1 is} alkyl ether or ester, it is preferred that the total number of carbon atoms in the unit is in the range of 2 to 22.

worin R₆ für Alkyl mit 3 bis 22 Kohlenstoffatomen steht und R₇ Wasserstoff oder Alkyl mit 1 bis 22 Kohlenstoffatomen bedeutet. Somit kann R₆ beispielsweise Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Uneicosyl, Doeicosyl oder ein Isomer hiervon sein, beispielsweise Isopropyl, Isobutyl, sek.-Butyl, tert.-Butyl, 2-Ethylhexyl und dergleichen. Es ist stärker bevorzugt, dass R₆ Alkyl mit 4 bis 18 Kohlenstoffatomen, insbesondere mit 4 bis 14 Kohlenstoffatomen, bedeutet. R₇ steht für Wasserstoff oder Alkyl mit 1 bis 22 Kohlenstoffatomen. Wenn R₇ Alkyl ist, kann es beispielsweise Methyl, Ethyl, Propyl, Butyl, Pentyl, Hexyl, Heptyl, Octyl, Nonyl, Decyl, Undecyl, Dodecyl, Tridecyl, Tetradecyl, Pentadecyl, Hexadecyl, Heptadecyl, Octadecyl, Nonadecyl, Eicosyl, Uneicosyl, Doeicosyl oder ein Isomer hiervon sein, beispielsweise Isopropyl, Isobutyl, sek.-Butyl, tert.-Butyl, 2-Ethylhexyl und dergleichen. Es ist bevorzugt, dass R₇ Wasserstoff oder Alkyl mit 1 bis 18 Kohlenstoffatomen bedeutet, insbesondere, dass R₇ Alkyl mit 1 bis 14 Kohlenstoffatomen bedeutet.When R _{5 is} a hindered phenolic group, it is preferably one having the following structure:

wherein R _{6 is} alkyl having 3 to 22 carbon atoms and R _{7 is} hydrogen or alkyl having 1 to 22 carbon atoms. Thus, R ₆ may be, for example, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl, doeicosyl or an isomer thereof, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl and the like. It is more preferred that R _{6 is} alkyl of 4 to 18 carbon atoms, especially 4 to 14 carbon atoms. R ₇ is hydrogen or alkyl of 1 to 22 carbon atoms. When R _{7 is} alkyl, it may be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, uneicosyl , Doeicosyl or an isomer thereof, for example, isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl and the like. It is preferred that R _{7 is} hydrogen or alkyl of 1 to 18 carbon atoms, especially that R _{7 is} alkyl of 1 to 14 carbon atoms.

In From the above structural formulas, m, n and p are independently from one another Numbers selected, which correspond to 0 or 1. By this is meant that the units in the parentheses that precede them, are either present, if a given integer is 1, or missing if the whole Number is 0. If m, n and p are all equal to 0, that reduces Structural formula on, for example:

• (A) die Verbindungen, worin R₁ und R₂ Wasserstoff bedeuten, z.B.
  
  und
• (B) die Verbindungen, worin R₁ für ein verzweigtes oder lineares C₁-C₂₂-Alkyl (oder -Alkylen) steht und R₂ ein primäres Alkylamin bedeutet, wie -CH₂CH₂-NH₂ oder -CH₂CH₂CH₂-NH₂, z.B.
  

The compounds may, in a preferred embodiment of the present invention, be divided into two groups based on their chemical structure, that is:

• (A) the compounds in which R ₁ and R _{2 are} hydrogen, for example
  
  and
• (B) the compounds wherein R _{1 is} a branched or linear C ₁ -C ₂₂ alkyl (or alkylene) and R _{2 is} a primary alkylamine, such as -CH ₂ CH ₂ -NH ₂ or -CH ₂ CH ₂ CH ₂ -NH ₂ , eg
  

These both compounds are from the same starting compounds of derived structure:

unter Bildung des Iminadduktzwischenprodukts, das anschließend zu dem Endprodukt katalytisch hydriert werden kann, hergestellt.Antioxidants of group (A) are prepared by catalytic reductive amination of the above starting compounds with ammonia and hydrogen. The antioxidants of group (B) are prepared by reacting the above starting compounds with an N-alkylcyanoalkylamine, for example, the N-alkylcyanoethylamine shown below

to form the imine adduct intermediate, which can then be catalytically hydrogenated to the final product.

As noted above, the N-aromatic substituted acid amide compounds of the present invention can be used as such or reacted with a carboxylic acid material attached to a substantially linear polymer, copolymer or terpolymer. The polymer backbone may be made of ethylene or propylene or it may be prepared from ethylene and at least one higher olefin in a range of C ₃ -C ₂₃ α-olefins.

Further instead of propylene to form the copolymer suitable or in combination with ethylene and propylene to form a terpolymer to be used α-olefins include 1-butene, 1-pentene, 1-hexene, 1-octene and styrene, α, ω-diolefins, such as 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, branched-chain α-olefins, such as 4-methylbutene-1,5-methylpentene-1 and 6-methylhepten-1, and mixtures hereof.

More complex polymer substrates, often referred to as copolymers, can be made using a third component. The third component commonly used to make a copolymer substrate is a polyene monomer made from non-conjugated dienes and Trienen is selected. The non-conjugated diene component is one having 5 to 14 carbon atoms in the chain. Preferably, the diene monomer is characterized by the presence of a vinyl group in its structure and may include cyclic and bicyclic compounds. Representative dienes include 1,4-hexadiene, 1,4-cyclohexadiene, dicyclopentadiene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 1,5-heptadiene and 1,6-octadiene. A mixture of more than one diene can be used in the preparation of the mixed polymer. A preferred non-conjugated diene for making a terpolymer or mixed polymer substrate is 1,4-hexadiene.

The Triene component has at least two non-conjugated double bonds and up to about 30 carbon atoms in the chain. Typical at trienes suitable for the preparation of the copolymer of the invention are 1-isopropylidene-3α, 4,7,7α-tetrahydroindene, 1-isopropylidenedicyclopentadiene, dihydroisodicyclopentadiene and 2- (2-methylene-4-methyl-3-pentenyl) [2.2.1] bicyclo-5-heptene.

Ethylene-propylene or higher alpha-olefin copolymers may comprise from about 15 to about 80 mole percent ethylene and from about 85 to about 20 mole percent of a C ₃ -C ₂₃ alpha-olefin, preferably from about 35 to 75 mole percent. Ethylene and about 65 to 25 mole% of the C ₃ -C ₂₃ alpha-olefin, more preferably 50 to 70 mole% of ethylene and 50 to 30 mole% of the C ₃ -C ₂₃ alpha-olefin, and in most preferably 55 to 65 mole% of ethylene and 45 to 35 mole% of the C ₃ -C ₂₃ α-olefin.

Terpolymer the above polymers can from about 0.1 to about 10 mole percent of the non-conjugated diene or triene contain.

The Ethylene copolymer or terpolymer substrate is an oil-soluble linear or branched polymer having a number average molecular weight from about 20,000 to about 150,000, as determined by gel permeation chromatography and universal calibration standardization, a preferred one number average molecular weight range between 30,000 and 110,000 lies.

The expressions Polymer and copolymer are used generically to form ethylene copolymers, Terpolymers or copolymers. These materials can be minor amounts contain other olefinic monomers, provided that the basic properties of ethylene copolymers are not material changed become.

The polymerization reaction used to form the ethylene-olefin copolymer substrate becomes common in the presence of a conventional one Ziegler-Natta or metallocene catalyst system performed. The Polymerization medium is not specific and can be solution, Slurry or gas phase processes, all known to one of ordinary skill in the art are, include. When the solution polymerization used, the solvent can any suitable inert hydrocarbon solvent be under the reaction conditions for the polymerization of α-olefins liquid is. examples for satisfactory hydrocarbon solvents include straight chain Paraffins of 5 to 8 carbon atoms, with hexane being preferred. Aromatic hydrocarbons, preferably aromatic hydrocarbons with a single benzene nucleus, such as benzene, toluene and the like, as well as saturated cyclic hydrocarbons having boiling point ranges corresponding to those the straight-chain paraffinic hydrocarbons described above and aromatic hydrocarbons are particularly suitable. The selected solvent may be a mixture of one or more of the above hydrocarbons be. When a slurry polymerization is used is the liquid Phase for the polymerization is preferably liquid propylene. It is desirable that the polymerization medium is free from substances containing the Disrupt catalyst components.

following becomes an ethylenically unsaturated Carboxylic acid material to the polymer backbone described above to form an acylated Ethylene copolymer grafted. These materials are used for grafting on the scaffolding contain at least one ethylenic bond and at least one, preferably two carboxylic acid or anhydride units or a polar group formed by oxidation or hydrolysis to a carboxylic acid group is convertible. Preferably, the carboxylic acid reactants are off the group selected, from acrylic, methacrylic, cinnamic, crotonic, maleic, fumaric and Itaconsäurereaktionsteilnehmern consists. In stronger Preferably, the carboxylic acid reactants are the group selected, made of maleic acid, fumaric acid, maleic anhydride and mixtures thereof. Maleic anhydride or a derivative this is generally the strongest preferred due to the commercial availability and simplicity of Reaction. In the case of unsaturated ethylenic copolymers or terpolymers is itaconic acid or an anhydride thereof is preferable because of its reduced tendency to form a crosslinked structure during the radical grafting process.

The ethylenically unsaturated Carboxylic acid materials can typically one or two carboxylic acid groups per mole of reactant provide with the grafted polymer. For example, methyl methacrylate a carboxylic acid group per molecule provide with the grafted polymer while maleic anhydride can provide two.

The carboxylic acid reactant is grafted onto the polymer backbone described in an amount to provide about 0.3 to 0.75 carboxylic acid groups per 1,000 number average molecular weight units of the polymer backbone, preferably about 0.3 to about 0.5 carboxylic acid groups per 1,000 number average molecular weight units. For example, a copolymer substrate with a M _n would of 20,000 with about 6 to about 15 carboxylic acid groups per polymer chain or about 3 to about 7.5 moles of maleic anhydride per mole of polymer grafted, while a copolymer having a M _n of 100,000 with about 30 to about 75 carboxylic acid groups per polymer chain or about 15 to about 37.5 moles of maleic anhydride per polymer chain would be grafted. The minimum level of functionality is the level required to achieve the minimum satisfactory dispersant performance. Beyond the maximum level of functionality, little, if any, additive dispersant performance is observed and other properties of the additive can be adversely affected.

The grafting reaction to form the acylated olefin copolymers is generally carried out using a free-radical initiator either in solution or in bulk, such as in an extruder or in an intensive mixer. When the polymerization is carried out in hexane solution, from the economical point of view, it is convenient to use the grafting reaction as described in U.S. Pat US 4 340 689 A . US Pat. No. 4,670,515 and US 4,948,842 A perform. The resulting polymer intermediate is characterized in that the carboxylic acid acylation functionality is randomly distributed throughout the structure of the polymer intermediate.

In the bulk process for preparing the acylated olefin copolymers, the rubber or plastic processing equipment, such as an extruder or masticator with the olefin copolymer, is heated to a temperature of about 150 ° C to about 400 ° C, resulting in co-charging of the ethylenically unsaturated carboxylic acid reactant and catalyst free radical initiator to the molten polymer to cause grafting. Optionally, the reaction may be carried out using mixing conditions which cause shearing and grafting of the ethylene copolymers, as described in U.S. Pat US 5 075 383 A is described. The processing apparatus is generally purged with nitrogen to prevent oxidation of the polymer and to assist in venting the unreacted reactants and by-products of the grafting reaction. The residence time in the processor is sufficient to provide the desired level of acylation and to ensure purification of the acylated copolymer via aeration. Optionally, a mineral or synthetic lubricating oil may be added to the processing apparatus after the aeration step to dissolve the acylated copolymer.

The radical initiator used for grafting the ethylenically unsaturated Carboxylic acid material on the polymer backbone can be used include peroxides, hydroperoxides, peresters and azo compounds, preferably those with a boiling point of more than 100 ° C, which are thermally decompose, leaving free radicals in the Pfropftererpaturbereich to be provided. Representative free-radical initiators include azobutyronitrile, dicumyl peroxide, 2,5-dimethylhexane-2,5-bis-tert-butyl peroxide and 2,5-dimethyl-3-yne-2,5-bis-tert-butyl peroxide. The starter will in an amount of between about 0.005% by weight and about 1% by weight on the weight of the reaction mixture used.

Other processes known in the art for effecting reaction of ethylene-olefin copolymers with ethylenically unsaturated carboxylic reagents, for example, halogenation reactions, thermal reactions or "ene" reactions, or mixtures thereof, may be used instead of the radical grafting process a mineral oil or in the mass by heating the reactants to temperatures of about 250 ° C to about 400 ° C under an inert atmosphere to prevent the generation of free radicals and oxidation byproducts. "En" reactions are a preferred method of grafting, if the ethylene-olefin copolymer contains unsaturated bonds. In order to achieve graft levels of from about 0.3 to about 0.75 carboxyl groups per 1000 M _n , it may be necessary to join or precede a radical grafting reaction to an "ene" or thermal grafting reaction.

The reaction between the carboxylic acid material bonded to a substantially linear polymer, copolymer or terpolymer and the N-aromatic substituted acid amide compounds of the present invention is generally accomplished by heating a solution of the polymer substrate under inert conditions and then adding the N-aromatic substituted amic acid compound to the heated solution mine with mixing to induce a reaction. Conventionally, an oil solution of the polymer substrate, which is heated to 140 ° C to 175 ° C while the solution is kept under an inert atmosphere or a nitrogen blanket, is used. The N-aromatic substituted acid amide compound is added to this solution and the reaction is carried out under the conditions indicated. The N-aromatic substituted acid amide compound may be added in one of two ways - blank or in a solution of a suitable carrier solvent capable of delivering the compound to the reaction vessel, such as oil, toluene or dinonylphenol.

Like in the US 4,990,274 A discloses it is possible to reduce the bulk viscosity of a mixture of a grafted and derivatized polymer in mineral oil by adding a minor amount of a cosolvent, such as an ethoxylated alcohol, polypropylene glycol or adipate diester. It has now been found that the addition of dinonylphenol also has the advantage of reducing the bulk viscosity of the final product. The cosolvent may be added before, together with or after the addition of the acid amide compound. Moreover, this effect is evident regardless of which is the derivatizing agent. Examples of other derivatizing agents are polyamines, hydroxyamines or polyols. Particularly suitable polyamines are those having 2 to 20 carbon atoms and 2 to 5 nitrogen atoms in the molecule, wherein only 1 nitrogen atom is a primary nitrogen atom and the remaining tertiary nitrogen atoms or highly hindered secondary nitrogen atoms. The class of suitable polyamines includes hydrocarbyl polyamines including alkyl, aryl and mixed alkaryl polyamines which may contain other groups such as hydroxy, oxyamide and imidazoline groups, N-phenylphenylenediamine, N-aminoalkylimidazole or N-aminoalkylmorpholine. Suitable hydroxyamines are these hydroxyamines having 2 to 20 carbon atoms, 1 to 4 hydroxy groups and 1 to 5 nitrogen atoms. Typical hydroxyamines include diethanolamine, dipropanolamine, trishydroxymethylaminomethane and 2-amino-2-ethyl-1,3-propanediol. Suitable polyols for the derivatization reaction are the polyols having 2 to 20 carbon atoms and having 2 to 5 hydroxyl groups. Typical polyols include glycerin and alkylene glycols such as dipropylene glycol and pentaerythritol.

The new invention grafted polymers are useful as additives for lubricating oils. They are multifunctional Additives for Lubricants that are effective to have dispersing properties, a viscosity index improvement and to provide antioxidant properties in lubricating oils. You can in a variety of oils an lubricating viscosity, including natural and synthetic lubricants and Mixtures thereof, to be used. The new additives can be added in Crankcase lubricating oils for spark-ignited and pressure-ignited Internal combustion engines are used. The compositions can also in gas engines or turbines, automatic transmission fluids, Gear lubricants, metalworking lubricants, hydraulic liquids and other lubricating oil and fat compositions. Their use in engine oil compositions is also considered.

For certain Applications, such as single-grade lubricating oils, may be desirable be to reduce the molecular weight of the polymers. The reduction the molecular weight of the starting ethylene copolymer having a molecular weight over 80,000 to a molecular weight in the range of 5,500 to 80,000 and the Grafting of the ethylenically unsaturated Carboxylic acid material on the copolymer can reached simultaneously or successively in any order become. When done sequentially, the ethylene copolymer first degraded to the predetermined molecular weight and subsequently grafting or vice versa can be grafting on the one high molecular weight copolymer, and the resulting, high molecular weight grafted copolymer can subsequently be reduced in molecular weight. alternative can grafting and reducing the high molecular weight Copolymers occur simultaneously.

The Reducing the molecular weight of a high molecular weight having ethylene copolymer to the predetermined molecular weight range occurs in the absence of a solvent or in the presence of a base oil using a mechanical shear agent. In general For example, the ethylene copolymer is brought to a molten state at a Temperature in the range of 250 ° C up to 450 ° C heated and subsequently subjected to mechanical shearing until the copolymer on the predetermined molecular weight range is reduced. The shear can be achieved by forcing the molten copolymer through fine openings under pressure or by other mechanical means.

The additives of the present invention may be used in combination with other additives typically found in lubricating oils, and such combinations may indeed have synergistic effects in terms of improving desired properties, such as improved deposition control properties, anti-wear properties, friction properties, anti-spattering properties Oxidation properties, low temperature properties and similar properties, provide the lubricating oil. The additives typically found in lubricating oils are dispersants, detergents, rust inhibitors, antioxidants, anti-wear agents, anti-foaming agents, friction modifiers, sealer swelling agents, demulsifiers, VI improvers, and pour point depressants (see, e.g. US 5 498 809 A for the description of suitable lubricating oil composition additives). Examples of dispersants include polyisobutylene succinimides, polyisobutylene succinate esters, ashless Mannich base dispersants, and the like. Examples of detergents include metal alkyl phenates, sulfurized metal alkyl phenates, metal alkyl sulfonates, metal alkyl salicylates, and the like. Examples of antioxidant additives that can be used in combination with the additives of the invention include alkylated diphenylamines, N-alkylated phenylenediamines, hindered phenolics, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidenebisphenols, oil soluble copper compounds, and the like. Examples of anti-wear additives which may be used in combination with the additives of the present invention include organoborates, organophosphites, organic sulfur-containing compounds, zinc dialkyldithiophosphates, zinc diaryldithiophosphates, phosphosulfurized hydrocarbons, and the like. Examples of friction modifiers that can be used in combination with the novel additives of the present invention include fatty acid esters and amides, organomolybdenum compounds, molybdenum dialkylthiocarbamates, molybdenum dialkyl dithiophosphates, and the like. An example of an anti-foaming agent is a polysiloxane and the like. An example of a rust inhibitor is a polyoxyalkylene polyol and the like. Examples of VI improvers include olefin copolymers and dispersing olefin copolymers, and the like. Examples of pour point depressants are polymethacrylate and the like.

in the General contains the lubricating oil composition according to the present Invention the new product in a concentration range of about 0.01 to about 30 wt .-%. A preferred concentration range for the additive is between about 1 and 15 wt .-%, based on the total weight the oil composition. Compositions containing these additives typically become in the base oil in amounts that are effective to their normal accompanying To provide functions. Representative effective amounts for Such additives are given by way of illustration below:

When other additives are used, it may be desirable, although not necessary, to prepare additive concentrates containing the concentrated solutions or dispersions of the subject additives of the present invention (in the above concentrate amounts) together with one or more of the other additives (this concentrate will be referred to herein it is an additive mixture, referred to as an additive package), whereby several additives can be simultaneously added to the base oil to form the lubricating oil composition. Dissolution of the additive concentrate in the lubricating oil may be facilitated by solvents or by mixing accompanied by mild heating, but this is not essential. The concentrate or additive package is typically formulated to contain the additives in suitable amounts to provide the desired concentration in the final formulation when the additive package is combined with a predetermined amount of a base lubricant. Thus, small amounts of base oil or other compatible solvents along with other desired additives may be added to the present additives of the present invention to form additive packages which contain effective ingredients in collective amounts of typically from about 2.5 to about 90 weight percent, preferably from about 15 to about 75 weight percent, more preferably from about 25 to about 60 weight percent additives in the appropriate proportions and the rest lubricating oil. The final formulations may typically use about 1 to 20% by weight of the additive package and the balance lubricating oil.

Oil concentrates of the additives may contain from about 1 to 50 weight percent of the additive reaction product in a vehicle or diluent oil of lubricating oil viscosity. If desired, the bulk viscosity of the oil concentrate may be adjusted by mixing a minor amount of a cosolvent with the concentrate as disclosed in U.S. Pat US 4,990,274 A be reduced.

All here indicated weight percentages (unless stated otherwise) are based on the content of active ingredients (Al) of the additive and / or the total weight of any additive package or formulation, which is the sum of the weight of active ingredients (Al) of a of each additive plus the weight of the total oil or diluent represents, based.

in the Generally, the lubricant compositions of the invention contain the additives in a concentration range of about 0.01 to about 30% by weight. A concentration range for the additives in the range of from about 0.01% to about 10% by weight, based on the total weight of the oil composition, is preferred. A preferred concentration range is between from about 0.2 to about 5 weight percent. Oil concentrates of Additives can from about 1 to about 75 weight percent of the additive reaction product in one carrier or diluent oil one Contain lubricating oil viscosity.

in the In general, the additives of the invention are useful in a variety of lubricating oil base materials. The lubricating oil base material is any natural or synthetic lubricating base oil feedstock fraction with a kinematic viscosity at 100 ° C from about 2 to 200 cSt, preferably from about 3 to 150 cSt, in particular about 3 to 100 cSt. The lubricating oil base material can be of natural Lubricating oils, synthetic lubricating oils or mixtures thereof. Suitable lubricating oil base materials include base materials obtained by isomerizing a synthetic Waxes and a wax, as well as hydrocracking base materials, which by hydrocracking (rather than by solvent extraction) the aromatic and polar components of the raw material. Natural lubricating oils include animal oils, vegetable oils (e.g. Rapeseed oils, castor and lard oil), Oil, mineral oils and coal or slate derived oils.

Synthetic oils include hydrocarbon oils and halo-substituted hydrocarbon oils, such as polymerized and copolymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl ethers, alkylated diphenyl ethers, alkylated diphenyl sulfides and their derivatives, analogs and homologs thereof, and the like. Synthetic lubricating oils further include alkylene oxide polymers, interpolymers, copolymers and derivatives thereof wherein the terminal hydroxyl groups have been modified by esterification, etherification, etc. Another suitable class of synthetic lubricating oils includes the esters of dicarboxylic acids with a variety of alcohols. Suitable synthetic oils include esters of C ₅ -C ₁₂ monocarboxylic acids and polyols and polyol ethers.

Silicon-based oils (For example, the polyalkyl, polyaryl, polyalkoxy or Polyaryloxysiloxanöle and silicate oils) Another suitable class of synthetic lubricating oils. Further synthetic lubricating oils include liquid Esters of phosphorus-containing acids, polymeric tetrahydrofurans, polyalphaolefins and the like.

The lubricating oil may be derived from unrefined, refined and refined oils or mixtures thereof. Unrefined oils are obtained directly from a natural source or synthetic source (eg, coal, shale or tar and bitumen) without further purification or treatment. Examples of unrefined oils include a shale oil obtained directly from a retorting operation, a petroleum oil obtained directly by distillation or an ester oil obtained directly from an esterification process, each of which is subsequently used without further purification. Refined oils are similar to unrefined oils except that the refined oils have been treated in one or more purification steps to improve one or more properties. Suitable purification techniques include distillation, hydrotreating, dewaxing, solvent extraction, acid or base extraction, filtration and percolation, all of which are known to those skilled in the art. Refined oils are obtained for treating refined oils in processes similar to those used to obtain the refined oils. These re-refined oils are also known as re-generated or re-processed oils and are often additionally obtained by means of tech processes to remove used additives or oil degradation products.

Oil-based feedstocks which result from the hydroisomerization of wax, may also be either alone or in combination with the natural and / or synthetic mentioned above Basic starting materials are used. Such wax isomerate oils are by the hydroisomerization of natural or synthetic Grow or mixtures thereof a hydroisomerization catalyst. Natural waxes are typically those obtained by the solvent dewaxing of mineral oils Slack waxes, synthetic waxes are typically the by the waxes produced by the Fischer-Tropsch process. The obtained Isomerate product will typically grow to a solvent and fractionate for obtaining various fractions with a specific viscosity range subjected. The wax isomerate is also characterized in that it has very high viscosity indices, generally with VI values of at least 130, preferably from at least 135 and above, and after dewaxing, a pour point of about -20 ° C or below has.

The additives according to the invention In particular, they are useful as components in many different lubricating oil compositions. The additives can in a variety of oils with lubricating viscosity including natural and synthetic lubricating oils and mixtures thereof. The additives can in Crankcase lubricating oils for spark-ignited and pressure-ignited Internal combustion engines be included. The compositions can also in gas engine lubricants, turbine lubricants, automatic transfer fluids, Gear lubricants, compressor lubricants, metalworking lubricants, hydraulic fluids and other lubricating oil and fat compositions. The additives can also in engine oil compositions be used.

The Advantages and important features of the present invention become more apparent from the following examples.

Example 1 N- (4-Anilinophenyl) -3 - [(3-aminopropyl) - (cocoalkyl) amino] butanamide

A Amount of 102.4 g (0.38 mol) of N- (4-anilinophenyl) -3-oxobutanamide, 91.6 g of N- (cocoalkyl) -3-aminopropanenitrile and 12 g of acid leached Bentonite clay was 48 h at 130 ° C touched. An equal volume of toluene was then added and the whole Refluxed for 30 min. Subsequently cooling took place, Filter and leave to stand over Night before being filtered again. The mixture was then washed with Raney cobalt catalyst and 800 psi hydrogen gas during 5 h at 110 ° C treated. The catalyst was filtered off and the solvent stripped under vacuum. The product (a viscous burgundy red oil) was added obtained in a yield of 133 g.

Example 2 3-Amino-N- (4-anilinophenyl) butanamide

30 g (0.11 mol) of N- (4-anilinophenyl) -3-oxobutanamide were dissolved in 300 ml of toluene. This solution was mixed with 30 g (1.8 mol) of anhydrous ammonia, Raney nickel catalyst and 800 psi of hydrogen gas at a temperature of 70 ° C for 2 hours. The catalyst was removed and the solvent stripped off under vacuum. Purification was by flash chromatography and recrystallization from hot toluene. The product was obtained in a yield of 16 g with a melting point of 130 to 132 ° C.

Example 3 3-Amino-N- (4-anilinophenyl) -N-isopropylbutanamide

The Example 3 became more similar Performed as example 2, wherein N- (4-anilinophenyl) -3-oxo-N-isopropylbutanamide was assumed. The product had a melting point of 145 up to 151 ° C.

The Starting materials for Examples 1, 2 and 3 can from the reaction product of diketene and acetoacetate ester and the derived corresponding amine.

Example 4

75 g of a maleic anhydride graft polymer (Rubber) wherein the polymer substrate is about 57 mole percent ethylene and 43 mole% propylene having a number average molecular weight from about 22,000, to the 2.9 weight percent maleic anhydride grafted in 225 g of lubricant diluent oil were heated with mechanical stirring to 160 ° C, while the Mixture was kept under a nitrogen blanket. As soon as the Temperature was reached, mixing was continued for an additional 1 h at 160 ° C.

11 g N- (4-anilinophenyl) -3 - [(3-aminopropyl) - (cocoalkyl) amino] butanamide, which were dissolved in toluene (42%) were added to the oil solution of Polymer was added and a reaction was for 4 h at 160 ° C under nitrogen carried out. The reaction mixture containing the derivatized graft polymer was subsequently chilled and filtered.

Example 5

75 g of a maleic anhydride graft polymer (Rubber) in which the polymer substrate consists of about 57% ethylene and 43% propylene with a number average molecular weight of about 22,000 was grafted onto the 2.9 wt .-% maleic anhydride in 225 g lubricant diluent oil were at 160 ° C with mechanical stirring heated while the mixture was kept under a nitrogen blanket. As soon as When the temperature was reached, mixing was continued for an additional 1 hour at 160 ° C.

A Amount of 5.98 g of pure 3-amino-N- (4-anilinophenyl) -N-isopropylbutanamide became the oil solution of Polymer added and the reaction for 4 h at 160 ° C under nitrogen carried out. 5 g of dinonylphenol were added as cosolvent was added and the reaction was stirred for a further 1 h. The The reaction mixture containing the derivatized graft polymer was subsequently chilled and filtered.

Example 6

A Amount of 31.25 g of a maleic anhydride graft polymer (Rubber), wherein the polymer substrate consists of about 57% ethylene and 43% propylene with a number average molecular weight of about 22,000 to which 2.9% by weight of maleic anhydride had been grafted in 88.75 g of lubricant diluent oil, was at 160 ° C with mechanical stirring heated while the mixture was kept under a nitrogen blanket. As soon as the temperature was reached, mixing for more Continued for 1 h at 160 ° C.

A Amount of 2.88 g of a pure 3-amino-N- (4-anilinophenyl) butanamide became the oil solution of Polymer was added and the reaction was for 4 h at 160 ° C under nitrogen carried out. 12 g of dinonylphenol was added as cosolvent was added and the reaction was stirred for a further 1 h. The Reaction mixture containing the derivatized graft polymer, was subsequently chilled and filtered.

oxidation test

Druckdifferentialabtast-Kalorimetrietest

PDSC formulation

The Additives were re their effectiveness in a motor oil formulation (see description in Table 1) and tested with identical Formulations with and without any zinc dialkyldithiophosphate (ZDDP) compared.

Table 1 SAE 10W-30 engine oil formulation (base mix)

Table 2 additive concentration

The Antioxidant properties of the new reaction products were determined in the pressure differential scanning calorimetry (PDSC) test. The PDSC conditions are given in Table 3. The PDSC data in Table 4 are a measure of Oxidation reduction time (OIT) of each mixture. All formulations were at 65 ° C while Mixed for 15 minutes under a nitrogen atmosphere. The PDSC method used a steel bomb under pressure. The catalyst is an oil-soluble one Iron derived from iron naphthenate. At the beginning of a test run the PDSC cell became initial at a rate of 40 ° C / min the isothermal temperature indicated in Table 3 is heated. The Induction time is from the time when the sample is its isothermal Temperature is reached until the enthalpy change is observed, measured. The longer the oxidation induction time is, the better the oxidation stability of the oil. The PDSC instrument used is a Mettler DSC27HP manufactured by Mettler-Toledo, Inc. was manufactured. The test has a repeatability of ± 2.5 min at 95% confidence interval for OIT's of less than 100 min. Each data point is the mean of two runs at a single test mix. A baseline result for the formulation in Table 1, which does not contain ZDDP or DCA-AO, could not be determined there the oil oxidized before reaching the test temperature of 175 ° C.

Table 3 PDSC test parameters

Table 4 PDSC results

Out From the above data it can be seen that the addition of these new reaction products improved the OIT of the base mixture in Table 1. As in example 18, there is a significant improvement in performance, that of a synergy between the reaction product and the ZDDP stems, when the new reaction products are used together with ZDDP.

Deposition control test

Thermooxidative engine oil simulation test (TEOST)

TEOST formulation

The Additives were re the effectiveness in a motor oil formulation (see description in Table 5) tested and with an identical Formulation compared.

Table 5 SAE 10W-30 engine oil formulation (base mix)

The Deposition control properties of the new reaction products were determined in the thermooxidative engine oil simulation test (TEOST). The test is used the amount of deposits formed by automotive engine oils be determined, and he will as a version of the ASTM test D6335-98 with an elevated Number of cycles to increase the rigor of the test.

at This test is a sample of engine oil at a temperature of 100 ° C, the Iron (III) naphthenate contains and in contact with nitric oxide and moist air, at to a given flow rate pumped past a tarred plating rod. The staff will be during the 9.5-minute temperature cycles ranging from 200 to 480 ° C, resistively. When all the cycles are over, the bar becomes oil residue rinsed and dried to get a gross mass. The oil sample will flushed out of the system and passed through a tarred filter. The deposition mass on the rod and the filter is the entire deposition mass. The capacity is typically given as total precipitate mass in mg on results measured between 10 and 100. The lower the number compared to the Comparison is, the better the performance of the oil formulation. Table 6 gives the parameters for the implementation of the TEOST test with the results for the mixture of the grafted and derivatized polymer in mineral oil samples (Examples 4, 5 and 5) 6) contained in Table 7 and the mean of two trial runs with two separate mixtures.

Table 6 TEOST parameters

Table 7 TEOST results

Out From the above data it can be seen that the addition of these new reaction products reduces the total deposition mass of the base formulation. For example, the addition of Example 4 reduces to the base mixture the deposition formation by about 55%.

Control of the volume viscosity

The Reduction of the high bulk viscosities of the oil solution of the grafted and derivatized Polymers are made by mixing a minor amount of the above cosolvent achieved with the copolymer. In general, has an oil concentrate from the grafted and derivatized polymer containing about 5 to 50 wt .-% of dissolved therein grafted and derivatized polymer and about 0.1 to 15% by weight the cosolvent, based on the total weight of the concentrate, contains substantially improved flow or fluidum properties for the concentrate mixture. A preferred amount of cosolvent in the concentrate mixture is an amount in the range of about 0.5 to 8 wt .-%, based on the total weight of the concentrate, with the most preferred Concentration of the cosolvent an amount in the range of about 2 to 5 wt .-% is. A flowable concentrate is by mixing in an effective or appropriate amount of cosolvent in the oil concentrate the final grafted and derivatized polymer or Copolymers obtained. The preferred cosolvent is an alkyl, dialkyl or mixed dialkylphenol, wherein each alkyl group is selected from the group selected is consisting of alkyl radicals having 6 to 22 carbon atoms, for example, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, Tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, Nonadecyl, eicosyl, uneicosyl, doeicosyl or isomers thereof. The strongest preferred dialkylphenol is dinonylphenol.

alternative can the flowable oil concentrate by using the cosolvent with the derivatizing compound before the reaction between the derivatizing compound and the grafted polymer become. Upon completion of the derivatization reaction, the result is a substantially improved flowable oil concentrate of the grafted and derivatized polymer.

Example 25

A Amount of 34.5 g of a maleic anhydride graft polymer (Rubber), wherein the polymer substrate consists of about 57% ethylene and 43% propylene with a number average molecular weight of about 30,200 whereupon 3.4% by weight of maleic anhydride was grafted into 103.5 g of lubricant diluent oil, was at 160 ° C with mechanical stirring heated while the mixture was kept under a nitrogen blanket. As soon as the temperature was reached, mixing for more Continued for 1 h at 160 ° C.

A Amount of 3.22 g of a pure 3-amino-N- (4-anilinophenyl) butanamide became the oil solution of Polymer was added and the reaction was for 4 h at 160 ° C under nitrogen carried out. The kinematic viscosity of the reaction mixture was then measured at 100 ° C and determined at 11,000 cSt.

dinonyl (5.6 g) was added as a cosolvent was added and the reaction was stirred for a further 1 h. The Reaction mixture containing the derivatized graft polymer, was subsequently cooled and filtered. Again, the kinematic viscosity of the reaction product became at 100 ° C measured and determined with 4,200 cSt.

Claims (15)

A chemical composition comprising an N-aromatic substituted acid amide compound selected from the group consisting of compounds of the formula:

wherein A and B are independently selected from alkylene groups; R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters; R _{2 is} hydrogen when R _{1 is} hydrogen; R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester; R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl; R _{5 represents} a sterically hindered phenol group,

wherein X is CH ₂ , S, NH or O, and m, n and p are independently selected from integers equal to 0 or 1; and wherein R _{5 is} a hindered phenol group of the following structure:

wherein R _{6 is} alkyl of 3 to 22 carbon atoms and R _{7 is} hydrogen or alkyl of 1 to 22 carbon atoms. A composition according to claim 1, wherein R _{5 is} for

stands. A composition according to claim 1, wherein n is 0. A composition according to claim 1, wherein n is 1 and A is propylene. A composition according to claim 1, wherein R ₁ and R _{2 are} both hydrogen. A composition according to claim 1, wherein R _{1 is other} than hydrogen and R _{2 is} a primary alkylamine. A composition according to claim 1, wherein m is 1 and B is methylene. A composition according to claim 1, wherein the N-aromatic substituted acid amide compound 3-amino-N- (4-anilinophenyl) -butanamide, 3-Amino-N- (4-anilinophenyl) -N-isopropylbutanamide or N- (4-anilinophenyl) -3 - {(3-aminopropyl) - (cocoalkyl) amino} butanamide is. A reaction product consisting of a carboxylic acid material bonded to a substantially linear polymer, copolymer or terpolymer further reacted with an N-aromatic substituted amic acid moiety, wherein the N-aromatic substituted acid amide moiety is selected from the group consisting of compounds of the following formula consists:

wherein A and B are independently selected from alkylene groups; R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters; R _{2 is} hydrogen when R _{1 is} hydrogen; R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester; R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl; R _{5 represents} a sterically hindered phenol group,

wherein X is CH ₂ , S, NH or O, and m, n and p are independently selected from integers equal to 0 or 1; and wherein R _{5 is} a hindered phenol group of the following structure:

wherein R _{6 is} alkyl having 3 to 22 carbon atoms and R _{1 is} hydrogen or alkyl having 1 to 22 carbon atoms. A lubricating oil composition comprising a major portion of lubricating oil and a minor proportion of an additive which is an N-aromatic substituted acid amide compound or the reaction product consisting of a carboxylic acid material bonded to a substantially linear polymer, copolymer or terpolymer; further reacted with an N-aromatic substituted acid amide unit, wherein the N-aromatic substituted acid amide is selected from the group consisting of compounds of the following formula:

wherein A and B are independently selected from alkylene groups; R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters; R _{2 is} hydrogen when R _{1 is} hydrogen; R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester; R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl; R _{5 represents} a sterically hindered phenol group,

wherein X is CH ₂ , S, NH or O, and m, n and p are independently selected from integers equal to 0 or 1; and wherein R _{5 is} a hindered phenol group of the following structure:

wherein R _{6 is} alkyl of 3 to 22 carbon atoms and R _{7 is} hydrogen or alkyl of 1 to 22 carbon atoms. Lubricating oil composition according to claim 10, further comprising a zinc dialkyldithiophosphate. A chemical composition comprising a solution comprising the following ingredients: (i) a reaction product consisting of a carboxylic acid material bonded to a substantially linear polymer, copolymer or terpolymer further reacted with an N-aromatic substituted acid amide moiety; the N-aromatic substituted acid amide unit is selected from the group consisting of compounds of the following formula:

wherein A and B are independently selected from alkylene groups; R ₁ is selected from the group consisting of hydrogen, alkyl, alkyl ethers or esters; R _{2 is} hydrogen when R _{1 is} hydrogen; R _{2 is} a primary alkylamine when R _{1 is} alkyl, alkyl ether or ester; R ₃ and R _{4 are} independently selected from the group consisting of hydrogen and alkyl; R _{5 represents} a sterically hindered phenol group,

or

wherein X is CH ₂ , S, NH or O, and m, n and p are independently selected from integers equal to 0 or 1; and (ii) an oil solvent, and wherein R _{5 is} a hindered phenol group of the following structure:

wherein R _{6 is} alkyl of 3 to 22 carbon atoms and R _{7 is} hydrogen or alkyl of 1 to 22 carbon atoms. A composition according to claim 12, wherein the oil solvent a mineral oil is. The composition of claim 12, further comprising cosolvents contains. A composition according to claim 14, wherein the cosolvent is an alkyl, dialkyl or mixed dialkylphenol, each Alkyl group selected is selected from the group consisting of alkylene of 6 to 22 carbon atoms.